EP1448568A2 - Dicops contenant des substituants acetyleniques - Google Patents

Dicops contenant des substituants acetyleniques

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Publication number
EP1448568A2
EP1448568A2 EP02786560A EP02786560A EP1448568A2 EP 1448568 A2 EP1448568 A2 EP 1448568A2 EP 02786560 A EP02786560 A EP 02786560A EP 02786560 A EP02786560 A EP 02786560A EP 1448568 A2 EP1448568 A2 EP 1448568A2
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EP
European Patent Office
Prior art keywords
bis
cyclopentadienyl
dimethyl
zirconium
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP02786560A
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German (de)
English (en)
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EP1448568A4 (fr
Inventor
George Rodriguez
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Publication of EP1448568A2 publication Critical patent/EP1448568A2/fr
Publication of EP1448568A4 publication Critical patent/EP1448568A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • This invention relates to polymerization cocatalyst compounds contain- ing weakly coordinating Group- 13 -element anions and to the preparation of olefin polymers using ionic catalyst systems based on organometallic transition-metal cationic compounds stabilized by these anions.
  • NCA noncoordinating anion
  • noncoordinating anions are described to function as electronic stabilizing cocatalysts, or counterions, for essentially active, cationic metallocene polymerization catalysts.
  • the term noncoordinating anion applies both to truly noncoordinating anions and to coordinating anions that are labile enough to undergo replacement by olefinically or acetylenically unsaturated molecules at the insertion site.
  • These noncoordinating anions can be effectively introduced into a polymerization medium as Bronsted acid salts containing charge-balancing countercations, as ionic cocatalyst compounds, or mixed with an organometallic catalyst before adding it to the polymerization medium. See also, the review articles by S. H. Strauss, "The Search for Larger and More Weakly Coordinating Anions," Chem. Rev., 93, 927-942 (1993).
  • U.S. Patent 5,502,017 addresses ionic metallocene polymerization catalysts for olefin polymerization containing a weakly coordinating an- ion comprising boron substituted with halogenated aryl substituents preferably containing silylalkyl substitution, such as a t-butyldimethyl-silyl substitution.
  • Marks et al. disclose the weakly coordinating anion as the cocatalyst.
  • the silylalkyl substitution is said to increase the solubility and thermal stability of the resulting metallocene salts.
  • Examples 3-5 describe synthesis of and polymerization with the cocatalyst compound triphenylcarbenium tetrakis (4-dimethyl-t- butylsilyl-2, 3, 5, 6-tetrafluorophenyl) borate.
  • Trifluoromethane- sulfonyloxy Derivatives of Tricyclohexylphosphine-Borane Syntheses, structural characterizations, and reactions of tricyclohexylphosphine- trifluoromethanesulfonyloxyborane and tricyclohexylphosphine- bis(trifluoromethanesulfonyloxy)-borane are described.
  • the invention provides cocatalyst compounds that can be combined with catalyst precursor compounds to form active catalysts for olefin insertion, coordination, or carbocationic polymerization, as well as catalyst systems containing such cocatalyst compounds.
  • cocatalyst compound is interchangeable with “cocatalyst activator compound” and “activator”).
  • Olefin polymerization can proceed by catalyst formation followed by, or in situ catalyst formation essentially concurrent with, contacting the catalyst with appropriate molecules: those having accessible, olefinic or acetylenic unsaturation or having olefinic unsaturation capable of cationic polymerization.
  • an appropriate olefin is one that is polymerizable by a catalyst system that uses the invention cocatalyst compounds.
  • the catalysts according to the invention are suitable for preparing polymers and copolymers from olefinically and acetyleni- cally unsaturated molecules.
  • Some invention embodiments select the cocatalyst to be neutral with three fluoroaryl ligands, while others select the cocatalyst to be ionic with four fluoro- aryl ligands. Some embodiments select the aryl ligand (otherwise known as a ring assembly) so that it comprises at least one fluorine group.
  • the cocatalyst comprises a Group-13 element bound to fluoroaryl ligands in which at least one fluoroaryl ligand is substituted with at least one acetylenic group: (BULKY-CC-).
  • BULKY represents a group that is bulky enough to kinetically or thermodynamically impede reaction of the acetlylenic group with the activated metallocene catalyst.
  • the neutral cocatalyst is itself the ligand abstracting moiety. Upon catalyst activation, the neutral cocatalyst becomes an NCA.
  • at lest one aryl ligand is substituted with at least one fluorine atom (i.e. fluoro substituted).
  • the cocatalyst contains a cationic, ligand-abstracting moiety
  • an activating cation and an NCA moiety comprising a Group-13 element bound to aryl ligands in which at least one aryl ligand is substituted with at least one acetylenic group: (BULKY-CC-).
  • Some embodiments select a triispropylsilylacetylenic substitution on each aryl ligand. Some embodiments select the Group-13 element to be boron. Some embodiments select the aryl ligands so that, other than acetylenic groups, the aryl ' ligand or ring assembly is perfluorinated.
  • the ligand-abstracting moiety can abstract an alkyl group from, or break a carbon-metal bond in, an organometallic compound (i.e., the catalyst precursor) upon contact with that compound. This process leaves a cationic catalyst, a neutral compound, and an NCA.
  • This invention relates to a composition of matter that contains an anionic central core wherein the anionic central core comprises a Group-13 atom.
  • This group-13 atom is connected to four ring assemblies wherein at least one ring as- sembly comprises an acetylene moiety.
  • This invention also relates to a composition of matter that contains a nuetral central core comprising a Group-13 atom. This atom is connected to three ring assemblies wherein at least one ring assembly comprises an acetylene moiety.
  • this invention relates to methods for using these composi- tions and to products produced using them.
  • Catalyst system encompasses a catalyst precursor/activator pair.
  • catalyst system When catalyst system is used to describe such a pair before activation, it means the un- activated catalyst together with the activator.
  • catalyst system When catalyst system is used to describe such a pair after activation, it means the activated catalyst and the NCA or other charge-balancing moiety. In some cases, catalyst refers to the activated catalyst.
  • NCA comprising an acetylene sub- stituent, as shown in the following formula.
  • the filled circle represents a bulky group that is large enough to impede or slow down access by the active site of the metallocene to the olefinic unsatura- tion of the acetylenic group.
  • a more specific representation is shown below.
  • R 3 Si represents the bulky group.
  • the acetylene substitution comprises a bulky group and an acetylenic group.
  • Si is silicon.
  • Each R is an organic radical and can be the same or different. At least one R is selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, 1-pentyl, 1-methylbut-l-yl, 2-methylbut-l-yl, 3-methylbut-l-yl, 2-pentyl, 3-pentyl, 1,1- dimethylprop-1-yl, 1,2-dimethylprop-l-yl, and 2,2-dimethylprop-l-yl.
  • R can also be selected from the isomers of the hexyl, heptyl, and octyl radicals.
  • exemplary silyl groups include the following Octadecyldimethylsilyl, (3-cyanopropyl) dimethylsilyl, (pen- tafluoropheny l)dimethylsily 1, (3 -chloropropyl)dimethylsilyl, ally ldimethylsilyl, butyldimethylsilyl, (chloromethyl)dimethylsil, decyl-dimethyl-silyl, diisopropyl- silyl, diisopropyloctylsilyl, dimethyl(3,3,3-trifluoropropyl)silyl, dimethyl(3,3,4,4, 5,5,6,6,6-nonafluorohexyl)silyl, dimethyldodecy
  • the isopropylsilylacetylenic group has the formula shown below. It can be more formally called the 2-(triisopropylsilyl)ethynyl or ethyn-1-yl radical.
  • One aspect of this invention is an NCA comprising the acetylenic groups discussed above connected to an aryl group.
  • the resulting assembly then ligates or connects to a Group-13 element (Group-13 elements are sometimes referre,d to as triels and abbreviated as Tr).
  • Group-13 elements are sometimes referre,d to as triels and abbreviated as Tr).
  • Some embodiments select the triel or Group-13 element to be B or Al.
  • Some embodiments select the aryl group to be fluorinated or perfluorinated.
  • the previous term is interchangeable with tris ⁇ pentafluorophenyl ⁇ ⁇ 4-[2- (triisopropylsilyl)ethynyl]- tetrafluorophenyl ⁇ borate.
  • NCAs as shown above have the ethynic or acetylenic portion of the acetylenic group directly connected to the fluoroaryl ligand.
  • the ligands around the Group-13 atom serve to stabilize the ion's charge. Furthermore, the ligands control the degree of contact between the catalyst and cocatalyst. With appropriate NCA, these two effects combine to diminish the ionic attraction between the catalyst and cocatalyst.
  • the NCA can be an assembly in which the anionic charge spreads out over the molecule making the charge more diffuse. After catalyst activation, the cocatalyst should either be completely non-coordinating or coordinate weakly enough so that the anion does not substantially impede the monomer's access to the catalyst.
  • Phenyl, biphenyl, naphthyl, indenyl, anthracyl, fluorenyl, azulenyl, phe- nanthrenyl, and pyrenyl are suitable aryl radicals. Some embodiments select phenyl, biphenyl, or naphthyl as the aryl radicals.
  • Exemplary ArF ligands and ArF substituents useful in this invention specifically include the fluorinated spe- cies of these aryl radicals.
  • Perfluorinated aryl groups also function and include substituted ArF groups having substituents in addition to fluorine, such as fluorinated hydrocarbyl groups.
  • Perfluorinated means that each aryl hydrogen atom is substi- tuted with fluorine or fluorcarbyl substituents, e.g., trifluoromethyl, pentafluoro- ethyl, heptafluoro-isopropyl, tris(trifluoromethyl)silyltetrafluoroethyl, and bis(trifluoroethyl) (heptafluoropropyl)silyltetrafluoroethyl.
  • fluorine or fluorcarbyl substituents e.g., trifluoromethyl, pentafluoro- ethyl, heptafluoro-isopropyl, tris(trifluoromethyl)silyltetrafluoroethyl, and bis(trifluoroethyl) (heptafluoropropyl)silyltetrafluoroethyl.
  • any ligand choice or substitution pattern that minimizes the number of abstractable hydrogen is useful in this invention's practice.
  • suitable ligand choices and substitution patterns will depend somewhat on the selected catalyst. Not all hydrogen substituents must be fluorine-replaced as long as the remaining hydrogen substituents are substantially non-abstractable by the specific catalyst of the catalyst system. Substantially non-abstractable means that the hydrogen may be extractable but at levels low enough so that the degree of chain termination and catalyst poisoning remains below that which is commercially reasonable. Some embodiments target lesser levels of abstractability. Cocatalyst activators can effectively activate catalysts for solution, bulk, slurry, and gas phase polymerization processes.
  • Cation counterparts for invention noncoordinating anion salts include those known in the art for NCAs.
  • Various cation classes include nitrogen- containing cations such as in the anilinium and ammonium salts of U.S. Patent 5,198,401 and WO 97/35893; the carbenium, oxonium, or sulfonium cations of US patent 5,387,568; metal cations, e.g., Ag + ; the silylium cations of WO 96/08519; and those of the hydrated, Group-1 or -2 metal cations of WO 97/22635.
  • invention NCAs can come from neutral Lewis acids comprising a Group-13 metal or metalloid center and from one to three halogenated aryl ligands as described above for the invention.
  • Complementary ligands are selected from those known in the art for noncoordinating anions.
  • some cocatalyst embodiments are neutral and become anionic during the activation process. Two such examples are shown below.
  • an anionic cocatalyst reacts with the catalyst precursor leaving an activated cationic catalyst and a weakly coordinating anion.
  • the cocatalyst contains a cation. Activation occurs when that cation either abstracts a hydride, alkyl, or substituted alkyl ligand, Q, from the catalyst precursor or cleaves a metal-organic bond in the precursor.
  • Activation transforms the cation of the cocatalyst into a neutral molecule; the non-coordinating anion remains anionic. Activation also transforms the neutral catalyst precursor into a cationic catalyst, typically by abstracting a hydride or anionic alkyl, which combines with the proton from the cocatalyst.
  • acetylenic-substituted activators or cocatalysts may be prepared as follows.
  • Suitable catalyst precursor compounds for use in this invention include the known organometallic, transition metal compounds useful for traditional Ziegler-Natta polymerization, particularly the metallocenes known to be useful in polymerization.
  • the catalyst precursor must be susceptible to activation by in- vention cocatalysts.
  • Useful catalyst precursors include Group-3-10 transition metal compounds in which at least one metal ligand can be abstracted by the cocatalyst.
  • those abstractable ligands include hydride, hydrocarbyl, hy- drocarbylsilyl, and their lower-alkyl-substituted (Ci-Cio) derivatives. Examples include hydride, methyl, benzyl, dimethyl-butadiene, etc.
  • Abstractable ligands and transition metal compounds comprising them include those metallocenes described in, for example, U.S. Patent 5,198,401 and WO 92/00333. Syntheses of these compounds are well known from the published literature.
  • the metal ligands include labile halogen, amido, or alkoxy ligands (for example, biscyclopentadienyl zirconium dichloride), which may not al- low for ready abstraction by invention's cocatalysts
  • the ligands can be replaced with abstractable ones. This replacement uses known routes such as alkylation with lithium or aluminum hydrides, alkyls, alkylalumoxanes, Grignard reagents, etc. See also EP 0 500 944 and EP 0 570 982 for the reaction of organoaluminum compounds with dihalo-substituted metallocenes prior to catalyst activation.
  • Such metallocenes can be described as mono- or biscyclopentadi- enyl-substituted Group-3, -4, -5, or -6 transition metals.
  • the transition metal ligands may themselves be substituted with one or more groups, and the ligands may bridge to each other or bridge through a heteroatom to the transition metal.
  • cyclopentadienyl rings including substituted, cyclopentadienyl-based, fused-ring systems, such as indenyl, fluorenyl, azulenyl, or their substituted analogs
  • the cyclopentadienyl rings when bridged to each other, are lower-alkyl substituted (Ci-C ⁇ ) in the 2 position (with or without a similar 4-position substituent in the fused ring are useful).
  • the cyclopentadienyl rings may additionally comprise alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl substituents, the latter as linear, branched, or cyclic structures including multi-ring structures, for example, those of U.S. Patents 5,278,264 and 5,304,614.
  • substituents should each have essentially hydrocarbyl characteristics and will typically contain up to 30 carbon atoms, but may contain heteroatoms, such as 1 to 5 non-hydrogen or non-carbon atoms, e.g., N, S, O, P, Ge, B and Si.
  • Invention activators are useful with essentially all known metallocene catalyst that are suitable for preparing polyolefins from C 2 -C ⁇ o ⁇ -olefin monomer or mixtures of monomers, see again WO-A-92/00333 and U.S. Patents 5,001,205, 5,198,401, 5,324,800, 5,304,614 and 5,308,816, for specific listings. Criteria for selecting suitable metallocene catalysts for making polyethylene and polypropylene are well known in the art, in both patent and academic literature, see for example Journal of Organometallic Chemistry 369, 359-370 (1989). Likewise, methods for preparing these metallocenes are also known.
  • the catalysts are stereorigid, asymmetric, chiral, or bridged-chiral metallocenes. See, for ex- ample, U.S. Patent 4,892,851, U.S. Patent 5,017,714, U.S. Patent 5,296,434, U.S.
  • Representative metallocene compounds can have the formula:
  • M is a Group-3-10 metal
  • LA is a substituted or unsubstituted, cyclo- pentadienyl or heterocyclopentadienyl ligand connected to M
  • L ⁇ is a ligand as defined for LA, or is J, a heteroatom ligand connected to M.
  • LA and LB may connect to each other through a Group-13- 16-element-containing bridge.
  • LQ is an optional, neutral, non-oxidizing ligand connected to M (i equals 0 to 3); and D and E are the same or different labile ligands, optionally bridged to each other, LA, or L ⁇ .
  • D and E are connected to M.
  • D and E's identity is functionally constrained.
  • the first constraint is that upon activation, either the D — M or the E — M comiection must break. D and E should be chosen to facilitate this.
  • Another constraint is that a polymerizable molecule must be able to insert between M and whichever of D or E remains.
  • Cyclopentadienyl and heterocyclopentadienyl ligands encompass fused- ring systems including but not limited to indenyl and fluorenyl radicals. Also, the use of heteroatom-containing rings or fused rings, where a non-carbon, Group-13, -14, -15, or -16 atom replaces a ring carbon is within the term "cyclopentadienyl" for this specification. See, for example, the background and illustrations of WO 98/37106, having priority with U.S. Ser. No. 08/999,214, filed 12/29/97, and WO 98/41530, having priority with U.S. Ser. No. 09/042,378, filed 3/13/98.
  • Substituted cyclopentadienyl structures are structures in which one or more hydrogen atoms are replaced by a hydrocarbyl, hydrocarbylsilyl, or similar heteroatom- containing structure.
  • Hydrocarbyl structures specifically include -C 30 linear, branched, and cyclic alkyl, and aromatic fused and pendant rings. These rings may also be substituted with ring structures.
  • Catalyst precursors also include the mono- and biscyclopentadienyl compounds such as those listed and described in U.S. Patents 5,017,714, 5,324,800, WO 92/00333 and EP-A-0 591 756.
  • Bis amide catalyst precursors are useful with invention cocatalysts.
  • Bisamide catalyst precursors are those precursors that have the following formula:
  • M is Ti, Zr, or Hf.
  • R are the same or different alkyls, aryls, substituted alkyl, or substituted aryls.
  • X are the same or different alkyls, aryls, or halides.
  • Substituted alkyl and aryls can be alkyl-, aryl-, and halo-substituted.
  • the bisamide catalyst precursor When X is a halide, the bisamide catalyst precursor must first be chemically modi- fied to transform X into an abstractable ligand. This can be done by alkylation, for example.
  • Pyridine bisamide catalyst precursors are also useful with invention cocatalysts.
  • Pyridine bisamide catalyst precursors are those precursors that have the following formula:
  • M is Ti, Zr, or Hf.
  • R are the same or different alkyls, aryls, substituted alkyl, or substituted aryls.
  • X are the same or different alkyls, aryls, or halides.
  • Substituted alkyl and aryls can be alkyl-, aryl-, and halo-substituted.
  • X is a halide
  • the pyridine bisamide catalyst precursor must first be chemically modified to transform X into an abstractable ligand. This can be done by alkylation, for example.
  • Amine bisamide catalyst precursors are also useful with invention cocatalysts.
  • Amine bisamide catalyst precursors are those precursors that have the following formula:
  • M is Ti, Zr, or Hf.
  • R and R' are the same or different alkyls, aryls, substituted alkyl, or substituted aryls.
  • X are the same or different alkyls, aryls, or halides.
  • Substituted alkyl and aryls can be alkyl-, aryl-, and halo-substituted.
  • X is a halide
  • the amine bisamide catalyst precursor must first be chemically modified to transform X into an abstractable ligand. This can be done by alkylation, for example.
  • Additional exemplary metallocene-type catalysts include those metallocene compounds represented by the formula:
  • M ⁇ is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten.
  • R! and R ⁇ are identical or different and are selected from hydrogen atoms, Cj-Cio alkyl groups, CJ-CJO alkoxy groups, C ⁇ -Cio aryl groups, C ⁇ -Cio aryloxy groups, C2-C10 alkenyl groups, C2-C40 alkenyl groups, C7-C40 arylal- kyl groups, C7-C40 alkylaryl groups, Cg-C4o arylalkenyl groups, OH groups or halogen atoms; or conjugated dienes that are optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups.
  • the conjugated diene can contain up to 30 atoms not counting hydrogen.
  • R3 are the same or different and are selected from hydrogen atom, halogen atoms, C ⁇ -Cio halogenated or unhalogenated alkyl groups, C6-C10 halogenated or unhalogenated aryl groups, C2-C10 halogenated or unhalogenated alkenyl groups, C7-C40 halogenated or unhalogenated arylalkyl groups, C7-C40 halogen- ated or unhalogenated alkylaryl groups, Cg-C4o halogenated or unhalogenated arylalkenyl groups, -NR'2, -SR', -OR , -OSiR'3 or -PR'2 radicals in which R is one of a halogen atom, a CJ-CIQ alkyl group, or a Cg-CjQ ar yl group.
  • R4 to R are the same or different and are hydrogen, as defined for R ⁇ or two or more adjacent radicals R ⁇ to R ⁇ together with the atoms connecting them form one or more rings.
  • R 14 , R 15 and R 16 are each independently selected from hydrogen, halogen, C ⁇ -C 20 alkyl groups, C 6 -C 3 o aryl groups, C 1 -C 20 alkoxy groups, C 2 -C 20 alkenyl groups, C 7 -C 40 arylalkyl groups, C 8 -C 40 arylalkenyl groups and C -C 0 alkylaryl groups, or R 14 and R 15 , together with the atom(s) connecting them, form a ring; and M is selected from carbon, silicon, germanium and tin.
  • R 3 is represented by the formula:
  • R ⁇ to R ⁇ 4 are as defined for Rl and R ⁇ , or two or more adjacent radicals R ⁇ to R ⁇ 4 5 including R ⁇ 0 and R ⁇ l, together with the atoms connecting them form one or more rings; M ⁇ is carbon, silicon, germanium, or tin.
  • Non-limiting representative catalyst precursor compounds include the following compounds: pentamethylcyclopentadienyltitanium isopropoxide; penta- methylcyclopentadienyltribenzyl titanium; dimethylsilyltetramethyl-cyclopenta- dienyl-t-butylamido titanium dichloride; pentamethylcyclopentadienyl titanium trimethyl; dimethylsilyltetramethylcyclopentadienyl-t-butylamido zirconium dimethyl; dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dihy- dride; dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dimethyl; unbridged biscyclopentadienyl compounds such as bis(l-methyl; 3-butylcyclo- pentadienyl)zirconium dimethyl; (pentamethyl
  • Additional compounds suitable as olefin polymerization catalysts for use in this invention will be any of those Group-3-10 compounds that can be converted by ligand abstraction or bond scission into a cationic catalyst and stabilized in that state by a noncoordinating or weakly coordinating anion sufficiently labile to be displaced by an olefinically unsaturated molecules such as ethylene.
  • Exemplary compounds include those described in the patent literature. International patent publications WO 96/23010, WO 97/48735 and Gibson, et al, Chem. Comm., pp. 849-850 (1998), which disclose diimine-based ligands for Group-8 to -10 compounds that undergo ionic activation and polymerize oleflns.
  • Group-11 catalyst precursor compounds, activable with ionizing cocatalysts, useful for olefin and vinylic polar molecules are described and exemplified in WO 99/30822 and its priority documents, including U.S. Patent Application Ser. No. 08/991,160, filed 16 December 1997.
  • U.S. Patent 5,318,935 describes bridged and unbridged, bisamido catalyst compounds of Group-4 metals capable of ⁇ -olefins polymerization.
  • Bridged bis(arylamido) Group-4 compounds for olefin polymerization are described by D. H. McConville, et al., in Organometallics 1995, 14, 5478-5480. Synthetic meth- ods and compound characterization are presented. Further work appearing in D.
  • a monoanionic bidentate ligand and two monoanionic ligands stabilize those catalyst precursors, which can be activated with this invention's ionic cocatalysts.
  • the catalyst system will generally employ one or more scavenging agents to remove polar impurities from the reaction environment and to increase catalyst activity.
  • Any polymerization reaction components particularly solvents, monomers, and catalyst feedstreams, can inadvertently introduce impurities and adversely affect catalyst activity and stability. Impurities decrease or even eliminate catalytic activity, particularly with ionizing- anion-activated catalyst systems.
  • Polar impurities, or catalyst poisons include water, oxygen, metal impurities, etc. These impurities can be removed from or reduced in the reaction components before their addition to the reaction vessel. Impurities can be removed by chemically treating the components or by impurity separation steps. Such treatment or separation can occur during or after synthesis of the components.
  • the polymerization process will normally employ minor amounts of scavenging agent.
  • these scavengers will be organometallic such as the Group-13 compounds of U.S. Patents 5,153,157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132, and that of WO 95/07941.
  • Exemplary compounds include triethyl aluminum, triethyl borane, tri- isobutyl aluminum, methylalumoxane, and isobutyl alumoxane.
  • Those compounds having bulky or C 5 -C 20 linear hydrocarbyl substituents connected to the metal or metalloid center are preferred because they coordinate to the active catalyst more weakly.
  • Examples include triethylaluminum and bulky compounds such as triisobutylaluminum, triisoprenylaluminum, and long-chain, linear-alkyl- substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n- octylaluminum, or tri-n-dodecylaluminum.
  • alumoxane is used as activator, any excess over that needed to activate the catalyst can act as a scavenger and additional organometallic scavengers may be unnecessary.
  • Alumoxanes also may be used as scavengers with other activators, e.g., methylalumoxane and triisobutyl- alumoxane with boron-based activators.
  • the scavenger amount is limited to that amount effective to enhance activity (and with that amount necessary for activation when used in a dual role) since excess amounts may act as catalyst poisons.
  • This invention's catalyst systems can polymerize those unsaturated molecules conventionally recognized as polymerizable using metallocenes.
  • Typical conditions include solution, slurry, gas-phase, and high-pressure polymerization.
  • the catalysts may be supported on inorganic oxide or polymeric supports and as such will be particularly useful in those operating modes employing fixed-bed, moving-bed, fluid-bed, slurry, or solution processes conducted in single, series, or parallel reactors.
  • Invention cocatalysts may also function in catalyst pre-poly- merization.
  • WO 98/55518 describes a support method for gas-phase or slurry polymerization.
  • Alternative invention embodiments employ the catalyst system in liquid phase (solution, slurry, suspension, bulk phase, or combinations thereof), in high- pressure liquid or supercritical fluid phase, or in gas phase. These processes may also be employed in singular, parallel, or series reactors.
  • the liquid phase processes comprise contacting olefin molecules with the catalyst system described above in a suitable diluent or solvent and allowing those molecules to react long enough to produce the invention polymers.
  • the term polymer encompasses both homo- and co-polymers. Both aliphatic and aromatic hydrocarbyl solvents are suitable; some embodiments select hexane.
  • the supported catalysts typically contact a liquid monomer slurry.
  • Gas-phase processes use a supported catalyst and follow any manner suitable for ethylene polymerization, although, some embodiments select the maximum pressure to be as low as 1600 or 500.
  • Illustrative examples may be found in U.S. Patents 4,543,399, 4,588,790, 5,028,670, 5,382,638, 5352,749, 5,408,017, 5,436,304, 5,453,471, and
  • the minimum, polymerization reaction temperature is 40°C. Some embodiments select the minimum reaction temperature to be 60°C. The temperature can go as high as 250°C, but some embodiments choose not to exceed 220°C. The minimum reaction pressure is 0.001 bar; although, some embodiments choose the minimum pressure to be as high as 0.1 or 1.0 bar. The maximum pressure is less than or equal to 2500 bar.
  • Invention catalyst systems can produce various polyethylenes including high- and ultra-high-molecular weight polyethylenes. These polyethylenes can be either homopolymers or copolymers with other ⁇ -olefins or ⁇ -olefmic or non- conjugated diolefins, e.g. C -C 20 olefins, diolef ⁇ ns, or cyclic olefins. In some embodiments, a low pressure (typically ⁇ 50 bar) vessel is used. Invention activated catalysts are slurried with a solvent (typically hexane or toluene).
  • a solvent typically hexane or toluene
  • the polyethylenes are produced by adding ethylene, and optionally one or more other mono- mers, along with the slurried catalyst to the low pressure vessel.
  • the temperature is usually within the 40-250 °C range. Cooling removes polymerization heat.
  • Gas-phase polymerization can be conducted, for example, in a continuous fluid- bed, gas-phase reactor operated at a minimum of 2000 kPa and up to 3000 kPa. The minimum temperature is 60°C; the maximum temperature is 160°C.
  • the gas- phase reaction uses hydrogen as a reaction modifier at a concentration of no less than 100 PPM. The hydrogen gas concentration should not exceed 200 PPM.
  • the reaction employs a C 4 - Cs comonomer feedstream and a C 2 feedstream.
  • the C 4 - Cg feedstream goes down to 0.5 mol%. It also may go up to 1.2 mol%. Finally, the C 2 feedstream has a minimum concentration of 25 mol%. Its maximum con- centration is 35 mol%. See, U.S. Patents 4,543,399, 4,588,790, 5,028,670 and
  • High-molecular-weight, low-crystallinity, ethylene- -olef ⁇ n elastomers can be prepared using invention catalyst systems under traditional solution processes or by introducing ethylene into invention catalyst slurries with ⁇ -olefin, cyclic olefin, or either or both mixed with other polymerizable and non-polymerizable diluents.
  • Typical ethylene pressures range from 10 to 1000 psig (69-6895 kPa) and the diluent temperature typically remains between 40 and 160 °C.
  • the process can occur in one or more stirred tank reactors, operated individually, in series, or in parallel.
  • the general disclosure of U.S. Patent 5,001,205 illustrates general process conditions. See also, international application WO 96/33227 and WO 97/22639.
  • invention catalyst systems for example, styrene, alkyl-substituted styrenes, isobutylene and other geminally disubstituted olefins, ethylidene norbor- nene, norbornadiene, dicyclopentadiene, and other olefinically-unsaturated molecules, including other cyclic olefins, such as cyclopentene, norbornene, alkyl- substituted norbornenes, and vinylic polar, polymerizable molecules. See, for example, U.S. Patents 5,635,573, 5,763,556, and WO 99/30822.
  • ⁇ - olefin macromers of up to 1000 mer units or more may be copolymerized yielding branched olefin polymers.
  • activated cation catalysts for oligomeri- zation, dimerization, hydrogenation, olefin/carbon-monoxide copolymerization, hydroformulation, hydrosilation, hydroamination, and related reactions can be activated with invention cocatalysts.
  • the invention cocatalysts can activate individual catalysts or can activate catalysts mixtures for polymer blends. Adept monomer and catalyst selection yields polymer blends analogous to those using individual catalyst compositions. Polymers having increased MWD (for improved processing) and other benefits available from mixed-catalyst-system polymers can be achieved using invention cocatalysts.
  • Blended polymer formation can be achieved ex situ through mechanical blending or in situ through using mixed catalyst systems. It is generally believed that in situ blending provides a more homogeneous product and allows the blend to be produced in one step.
  • In-situ blending with mixed catalyst systems involves combining more than one catalyst in the same reactor to simultaneously produce multiple, distinct polymer products. This method requires additional catalyst synthesis, and the various catalyst components must be matched for their activities, the polymer products they generate at specific conditions, and their response to changes in polymerization conditions. Invention cocatalysts can activate mixed catalyst systems.
  • Example 1 Synthesis of HC 6 F 4 -CC-Si(i-Pr) 3 : Sonogashira methodology was employed for the coupling reaction. To 150 milliliters of triethylamine was added Pd(OAc) 2 (0.733 grams), P(C 6 H 5 ) 3 (2.55 grams), and Cul (0.880 grams). HC 5 F 4 Br (17.00 grams) was added to the mixture, followed by HCCTMS (15.00 grams). After 15 minutes of completing the additions, the mixture turned dark and precipitate was observed. After stirring at room temperature for 20 minutes, the reaction was refluxed for 20 hours. The solids were filtered off. The filtrate were taken up with 300 milliliters of diethylether and washed with 5% HC1 (aq).
  • Example 2 Synthesis of [Li(Et 2 O) 2 . 5 ][B(C 6 F 4 -CC-Si(i-Pr) 3 ) 4 ]: To a cold solution of HC 6 F 4 -CC-Si(i-Pr) 3 in diethylether was added BuLi (10 milliliters, 1.6 M, Aldrich). After 5 minutes the solution turned a pale green. The reaction was allowed to stir at -78 deg C for 1 hour. BC1 3 (4.0 milliliter, 1.0 M, Aldrich) was added. The reaction was stirred for 4 hours. The solvent was replaced with methylene chloride and the LiCl removed by filtration. The solvent was reduced and pentane was added to incipient cloudiness. The mixture was chilled overnight and the resulting white crystalline product collected by filtration (2.305 grams). 1H NMR (Tol -d8 , 25 deg C): 3.10 (q, 12H), 1.14 (m, 84)
  • Example 3 Synthesis of [DMAH][B(C 6 F 4 -CC-Si(i-Pr) 3 ) 4 ]: To a methylene chloride solution of [Li(Et 2 O) 2 . 5 ][B(C 6 F 4 -CC-Si(i-Pr) 3 ) 4 ] (2.281 grams) was added a solution of DMAHC1 (0.236 grams). The resulting LiCl was removed by filtration after stirring for 1 hour. The solvent volume was reduced and the prod- uct precipitated out with pentane. The resulting product is a white solid (1.851 grams).
  • Example 4 Polymerization reactions: The polymerization reaction of pro- pylene were carried out in a 1/2 liter, autoclave batch reactor operating at 60°C.
  • the catalyst used was bis(indenyl)dimethylsilyl hafnium dimethyl.
  • the polymerization solvent was hexanes, while the activation solvent was toluene.
  • Standard runs using [B(C 6 F 5 ) ][C 6 H 5 NMe 2 H] as the activating cocatalyst were carried out.
  • Trioctylaluminium was used as the scavenger in all runs (25 % wt).
  • the scavenger-catalyst mole ratios for these two reactions were less than 10.
  • the polymers were precipitated with isopropyl alcohol and dried in a vacuum oven at 75°C To constant weights. The polymer melting points were determine with DSC, while the molecular weights were measured by GPC.

Abstract

Cette invention concerne un activateur pour catalyseurs de polymérisation d'oléfines. Cet activateur se caractérise notamment en ce qu'il comprend un atome central du groupe 13 relié à au moins un noyau aryle fluoré lui même substitué avec un groupe silyle acétylénique. Selon les modes de réalisation, on trouve un activateur neutre, ou bien un activateur couplé à un anion avec cation abstracteur de ligand. Ces activateurs sont des molécules séparées.
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AU2002350027A1 (en) 2003-05-19
US6909008B2 (en) 2005-06-21

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